JP2004326094A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition suitable to forming a light shielding separator or a black matrix of an organic electroluminescent device or a liquid crystal display element. <P>SOLUTION: The positive photosensitive resin composition contains (a) alkali-soluble resin, (b) a quinonediazido compound, (c) a heat coloring compound which colors being heated and shows an absorption maximum at 350-700 nm, and (d) a compound having no absorption maximum at 350 to <500 nm and having an absorption maximum at 500-750 nm. The photosensitive resin composition forms a positive film in which portions exposed with UV forms are dissolved in an aqueous alkali solution and can give a cured film suitable for forming a light shielding separator or a black matrix of an organic electroluminescent device or a liquid crystal display element and having such a light shielding effect as an optical density of ≥0.3 and such a light resistance as an optical density retention of ≥50% after the lapse of 500 hours under light irradiation. By using the photosensitive resin composition for a light shielding separator or a black matrix, an organic electroluminescent device or a liquid crystal display element of high quality can be supplied. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a positive photosensitive resin composition suitable for forming a light-shielding separator or a black matrix of an organic electroluminescent device or a liquid crystal display device as a flat panel display.

  Non-light-emitting liquid crystal displays (LCDs) have become widespread as flat panel displays, but organic electroluminescent devices have high brightness as self-luminous displays and are being actively researched and developed because they can be used as full-color displays. .

  The organic electroluminescent device operates by applying a voltage between the first electrode and the second electrode facing each other or by flowing a current. At this time, since an electric field tends to concentrate on the edge portion of the electrode having a small radius of curvature, undesirable phenomena such as dielectric breakdown and generation of leak current are likely to occur at the edge portion.

  In order to suppress these phenomena, it is known that an edge portion of the first electrode is covered with an insulating layer (also referred to as a separator) (see Patent Document 1). This technique makes it possible to reduce the electric field concentration at the edge of the electrode. Further, the thickness of the insulating layer at the exposed boundary portion on the first electrode gradually increases as the distance from the boundary increases so that the organic insulating layer and the second electrode formed after the formation of the insulating layer are smoothly deposited. By increasing the thickness, that is, by forming the cross section into a forward tapered shape, it is possible to suppress electric field concentration at the edge portion of the electrode. Recently, attempts have been made to add carbon black to a non-photosensitive polyimide resin in order to increase the contrast in an organic electroluminescent device so that an insulating film and / or an element isolation structure has a light-shielding property (Patent Document 2). reference). Further, a specific black matrix material is an alkali-soluble resin obtained by condensing phenols and aldehydes, an acid-crosslinkable methylolated melamine compound, a photoacid generator, a specific dispersant, and a negative photosensitive material comprising a black pigment. Non-photosensitive material comprising a material (see Patent Document 3), a polyimide precursor vehicle and a solvent, a light absorbing dye or a mixture thereof, a carbon black pigment or a non-carbon black metal oxide pigment, and a Newton dispersant (Patent Documents 4 and 5). See).

  Generally, polyimide, novolak, acrylic resin, or the like is used for the insulating layer of the display. These resins include non-photosensitive, negative-type photosensitive, and positive-type photosensitive. In order to suppress electric field concentration at the edge of the electrode, the insulating layer is preferably a positive-type photosensitive resin. Usually, the effective radiation intensity into the coating film during exposure gradually decreases from the coating surface toward the bottom. Therefore, in the positive photosensitive resin from which the exposed portion is dissolved and removed, the shape of the exposed portion is more likely to be a forward taper than that of a negative type or non-photosensitive resin, and a forward tapered shape can be easily formed.

  As a positive photosensitive resin composition for a black matrix of an LCD, a method of adding a quinonediazide compound and a black pigment to an alkali-soluble resin composed of a novolak resin or a vinyl polymer (see Patent Document 6), and a method of shading an organic EL element As the non-conductive insulating film, there is a method of adding a quinonediazide compound and a colorant to an alkali-soluble resin composed of a novolak resin or a polymer of a radical polymerizable monomer (see Patent Document 7).

  However, the light-shielding positive photosensitive resin prepared by adding a coloring agent to the resin composition described above has an exposure wavelength range of 350 nm or more of a mercury lamp generally used as an exposure light source in order to have sufficient light-shielding properties. Since it has an absorption maximum at 450 nm, there is a problem that the exposure sensitivity is deteriorated.

  On the other hand, by including a novolak resin and a naphthoquinonediazide-based photosensitizer, and performing exposure and / or heat treatment, the light transmittance of the coating film is reduced to about 10% or less in a visible region (400 to 700 nm). (See Patent Document 8). In this method, by performing exposure and heat treatment, the light transmittance of the coating film can be reduced to about 10% or less in a visible region (400 to 700 nm), and cresol novolak resin and naphthoquinonediazide resin can be used as coloring means. A photoresist containing a photosensitizer is used.

As a specific method for imparting light-shielding properties to an insulating layer, there is a method of adding a heat-sensitive material and a color developer to a diazoquinone-novolak resin-based positive resist (see Patent Document 9). In this method, a heat-sensitive material that develops a black color by applying heat and a positive photosensitive resin in which a developer is added in advance are used, so the heat-sensitive material is in an unreacted state before exposure and is black. Therefore, the photosensitive resin does not have a light-shielding property and does not deteriorate the exposure sensitivity. However, a general thermosensitive material comprising a color developer and a color former has a color development temperature of 100 to 180 ° C., and has a problem in heat resistance at a final heat treatment temperature after pattern processing (generally, 200 ° C. or higher). . Therefore, the heat-sensitive material that has developed color undergoes discoloration due to the final heat treatment, and sufficient light-shielding properties cannot be obtained. In addition, when blackening is performed using a general heat-sensitive material group consisting of a developer and a color former, after the final heat treatment, there is a problem in light resistance, and the color may fade by prolonged visible light-ultraviolet light irradiation. In many cases, it is difficult to continue using it as a black matrix of a display device.
JP-A-11-97182 (pages 1-3) JP-A-11-273870 (pages 1-3) JP 2000-47378 A JP-A-10-232302, JP 2001-525561A JP-A-6-230215 (page 1-2) JP-A-2002-116536 (pages 1-3) JP-A-8-137098 (pages 2-3) JP-A-10-170715 (pages 2-4)

  In view of the above problems, the present invention provides a photosensitive resin composition capable of obtaining a light-shielding and light-resistant cured film suitable for forming a light-shielding separator or a black matrix of an organic electroluminescent element or a liquid crystal display element. It is.

      That is, the present invention relates to (a) an alkali-soluble resin, (b) a quinonediazide compound, (c) a thermochromic compound that develops color by heating and exhibits an absorption maximum at 350 nm or more and 700 nm or less, and (d) 350 nm or more and less than 500 nm. A photosensitive resin composition containing a compound having no absorption maximum and having an absorption maximum at 500 nm or more and 750 nm or less.

  According to the present invention, not only a positive type in which a portion exposed to ultraviolet light dissolves in an alkaline aqueous solution can be formed, but also an optical density suitable for forming a light-shielding separator or a black matrix of an organic electroluminescent element or a liquid crystal display element. Can be obtained, and a cured film having a light resistance of not less than 0.3 and an optical density retention of not less than 50% after 500 hours of irradiation with light can be obtained. When the photosensitive resin composition of the present invention is used for a light-shielding separator or a black matrix, a high-quality organic electroluminescent device or liquid crystal display element can be supplied.

  The component (a) in the present invention needs to be soluble in an aqueous alkali solution used as a developer. Examples of the alkali-soluble resin include, but are not limited to, a phenol resin, a polymer containing a radical polymerizable monomer having an alkali-soluble group, a polyimide precursor, a polyimide, and a polybenzoxazole precursor. The polymer desirably has an alkali-soluble group in the molecule. Since the type of the polymer in the present invention is excellent in heat resistance and exhibits excellent characteristics as a separator of an organic electroluminescent device, it is preferable that the amount of degassing at a high temperature of 200 ° C. or higher after heat treatment is small, such as polyimide and polyhydroxyamide. And a polyimide precursor such as polyamic acid or polyamic acid ester or a polybenzoxazole precursor.

  Examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.

  The phenolic resin that can be used in the present invention includes a novolak phenolic resin and a resol phenolic resin, and is obtained by polycondensation of various phenols alone or a mixture of plural kinds thereof with aldehydes such as formalin.

  Examples of the phenols constituting the novolak phenol resin and the resol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-dimethylphenol. , 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, , 4,5-trimethylphenol, methylenebisphenol, methylenebis-p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichloro Phenol m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α -Naphthol, β-naphthol and the like, which can be used alone or as a mixture of a plurality.

  Examples of aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc., in addition to formalin, and these can be used alone or as a mixture of a plurality of aldehydes.

  The preferred weight average molecular weight of the phenolic resin used in the present invention is in the range of 2,000 to 50,000, preferably 3,000 to 30,000 in terms of polystyrene using gel permeation chromatography. If the weight average molecular weight exceeds 50,000, developability and sensitivity tend to deteriorate, and if it is less than 2,000, the pattern shape, resolution, developability, and heat resistance tend to deteriorate.

  In order to synthesize a polymer containing a radical polymerizable monomer having an alkali-soluble group, the following monomers can be used. Radical polymerizable monomers having a phenolic hydroxyl group or a carboxyl group include, for example, o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and their alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester, Carboxy-substituted products; polyhydroxyvinylphenols such as vinylhydroquinone, 5-vinylpyrogallol, 6-vinylpyrogallol, and 1-vinylphloroglicinol; o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid Acids and their alkyl, alkoxy, halogen, nitro, cyano, amide, ester substitutions, methacrylic and acrylic acids, and their haloalkyl, alkoxy, halogen, nitro, cyano substitutions Divalent unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid and 1,4-cyclohexenedicarboxylic acid, and their methyl, ethyl, propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, phenyl, o-, m-, p-toluyl half ester and half amide are preferred.

  Of these, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, and their alkyl and alkoxy substituents are useful for patterning sensitivity, residual film ratio after resolution development, heat deformation resistance, solvent resistance, It is preferably used from the viewpoints of adhesion to the solution, storage stability of the solution, and the like. These can be used alone or in combination of two or more.

  Other radically polymerizable monomers include, for example, styrene, and α-, o-, m-, or p-alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, and ester-substituted styrene. Diolefins such as butadiene, isoprene and chloroprene; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, pentyl, methacrylic acid or acrylate, neopentyl, isoamylhexyl, cyclohexyl , Adamantyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, anthraquinonyl, piperonyl, salicyl, cyclohexyl, benzyl, phenesyl, cresyl, glycidyl, 1,1,1-trifluoroethyl, perfluoroethyl, perfluoro-n- Propyl, perfluoro-i-propyl, triphenylmethyl, tricyclo [5.2.1.0 2,6] decane-8-yl (common name: "dicyclopentanyl"), cumyl, 3- (N, N -Dimethylamino) propyl, 3- (N, N-dimethylamino) ethyl, furyl, furfuryl ester, methacrylic acid or acrylic acid anilide, amide, or N, N-dimethyl, N, N-diethyl, N , N-dipropyl, N, N-diisopropyl, anthranilamide, acrylonitrile, acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, N-phenyl Maleimide, N- (4-hydroxyphenyl) maleimide, N-methacryloylphthalimide N- acryloyl phthalimide and the like can be used. These can be used alone or in combination of two or more.

  Among them, styrene, and α-, o-, m-, and p-alkyl, alkoxy, halogen, and haloalkyl substituents of styrene; butadiene, isoprene; methyl, ethyl, and methacrylic acid or acrylic acid; Each ester of n-propyl, N-butyl, glycidyl and tricyclo [5.2.1.0 2,6] decane-8-yl provides sensitivity during patterning, residual film ratio after resolution development, and heat deformation. It is particularly preferably used from the viewpoints of properties, solvent resistance, adhesion to a base, storage stability of a solution, and the like. When a copolymer of a radical polymerizable monomer having a phenolic hydroxyl group and another radical polymerizable monomer is used as the alkali-soluble resin, a preferable ratio of the other radical polymerizable monomer is a radical polymerizable monomer having a phenolic hydroxyl group and another. Is preferably not more than 30% by weight, particularly preferably 5 to 20% by weight, based on the total amount of the radical polymerizable monomer. When a copolymer of a radically polymerizable monomer having a carboxyl group and another radically polymerizable monomer is used as the alkali-soluble resin, a preferable ratio of the other radically polymerizable monomer is, Is preferably 90% by weight or less, particularly preferably 10 to 80% by weight, based on the total amount of the radical polymerizable monomer. If the ratio of the radical polymerizable monomer exceeds the above-mentioned ratio with respect to the radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group, alkali development may be difficult.

  Solvents used for producing a polymer containing a radical polymerizable monomer having an alkali-soluble group include, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol monomethyl ether, propylene glycol Mo Propylene glycol monoalkyl ethers such as ethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol butyl ether acetate Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate; toluene, xylene and the like Aromatic hydrocarbons; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, and 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3 -Ethyl hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetatepropyl, methoxyacetatebutyl Chill, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2 -Butyl ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxypropionate Methyl onate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxypropion Butylate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Esters such as propyl and butyl 3-butoxypropionate. The use amount of these solvents is preferably 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw materials.

  The polymerization initiator used for producing a polymer containing a radical polymerizable monomer having an alkali-soluble group is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvalero Azo compounds such as nitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis- ( organic peroxides such as t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

  The preferred weight-average molecular weight of the polymer containing a radical polymerizable monomer having an alkali-soluble group is preferably 2,000 to 100,000, more preferably 3,000 to 50, in terms of polystyrene using gel permeation chromatography. 000, particularly preferably 5,000 to 30,000. If the weight average molecular weight exceeds 100,000, developability and sensitivity tend to deteriorate, and if it is less than 2,000, pattern shape, resolution, developability and heat resistance tend to deteriorate.

  These polymers containing a radical polymerizable monomer having an alkali-soluble group may be used alone or in combination of two or more. Further, a protective group may be introduced into a carboxyl group or a phenolic hydroxyl group before polymerization, and alkali-soluble resin may be synthesized by deprotection after polymerization to impart alkali solubility. Further, transparency or softening point in visible light may be changed by hydrogenation treatment or the like.

In the formula, R ¹ is a divalent to octavalent organic group having two or more carbon atoms, R ² is a divalent to hexavalent organic group having two or more carbon atoms, and R ³ and R ⁴ are the same And represents hydrogen or an organic group having 1 to 20 carbon atoms. R ⁵ is a divalent organic group, and X and Y are a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, an unsaturated hydrocarbon group having at least one organic group having 1 to 10 carbon atoms. And an organic group having at least one substituent selected from a hydrocarbon group, a nitro group, a methylol group, an ester group, a hydroxyalkynyl group, and a hydrocarbon group having 1 to 10 carbon atoms. n ranges from 5 to 100,000, m is an integer from 0 to 10, p and q are integers from 0 to 4, and r and s are integers from 0 to 2, respectively. p + q> 0.

  The alkali-soluble resin having the structural units represented by the above general formulas (1) to (5) as a main component in the present invention becomes a polymer having an imide ring, an oxazole ring, or another cyclic structure by heating or an appropriate catalyst. obtain. It is also a heat-resistant resin precursor whose heat resistance and solvent resistance are dramatically improved by having a ring structure.

  The general formulas (1) to (5) represent polyamic acid having a hydroxyl group, and the hydroxyl group makes the solubility in an aqueous alkali solution better than that of a polyamic acid having no hydroxyl group. In particular, a phenolic hydroxyl group is more preferable among the hydroxyl groups from the viewpoint of solubility in an aqueous alkali solution. In addition, by having 10% by weight or more of fluorine atoms in each of the general formulas (1) to (5), when developing with an aqueous alkali solution, the water repellency appears properly at the interface of the film. And so on. However, when the fluorine atom content exceeds 20% by weight, the solubility in an alkaline aqueous solution decreases, the organic solvent resistance of the polymer formed into a cyclic structure by heat treatment decreases, and the solubility in fuming nitric acid decreases. Not preferred. Therefore, it is preferable that the fluorine atom is contained in an amount of 10% by weight or more and 20% by weight or less.

R ¹ contained in the dicarboxylic acid units of the above general formulas (1) to (5) represents a structural component of an acid dianhydride, and represents a divalent to octavalent organic group having two or more carbon atoms. The acid dianhydride is preferably a trivalent or tetravalent organic group containing an aromatic ring or an aliphatic ring and having 0 to 2 hydroxyl groups and having 6 to 30 carbon atoms. R ¹ is preferably an organic group containing an aromatic ring or an aliphatic ring and having 0 to 2 hydroxyl groups and having 6 to 30 carbon atoms.

  Specific acid dianhydrides having no hydroxyl group include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3 , 3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride Anhydride, bis (2,3- Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (4- (4-amino Phenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic acid Dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- ( 3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoro Aromatic tetracarboxylic dianhydrides such as lopan dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, and cyclobutane tetraanhydride Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro- Aliphatic tetracarboxylic acids such as 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxyanhydride and "TDA100, Licarezin TMEG" (trade names, manufactured by Nippon Rika Co., Ltd.) Acid dianhydrides can be mentioned. Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Screw (3,4-di (Ruboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (3 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl ) -4,4'-Bis (3,4-dicarboxyphenoxy) biphenyl dianhydride is preferred.

  When the compound has a hydroxyl group, examples of preferred compounds include those having the structures shown below, but are not limited thereto.

  These are used alone or in combination of two or more.

R ² contained in the diamine units of the general formulas (1) to (5) represents a divalent to hexavalent organic group having two or more carbon atoms. R ² is preferably an organic group having 6 to 30 carbon atoms containing an aromatic ring or an aliphatic ring. As a preferred example, a polymer having an aromatic property is preferable because of the heat resistance of the obtained polymer. Specific examples of the diamine having no hydroxyl group include 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, and 3,4′-diamine. Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m- Phenylenediamine, P-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, Bis (4-aminophenoxy) biphenyl, bis {4- ( -Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diamino Biphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or an aromatic ring thereof Examples include, but are not limited to, compounds substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like. The above compounds may be used alone or as a mixture of two or more.

When having a hydroxyl group, 2,2-bis [4- (amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl having a fluorine atom Hexafluoropropane, having no fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine and "ABCH", "ABPS" (trade name, Nippon Kayaku Co., Ltd.) Although R ² of Ltd.) compounds and formula such as (1) to (5) include a structure as shown below, but not limited to.

  These are used alone or in combination of two or more.

  The heat-resistant resin precursor represented by the general formulas (1) to (5) of the present invention can be prepared, for example, by reacting a tetracarboxylic dianhydride with a diamine compound at room temperature to 80 ° C. for 1 to 8 hours. A method of obtaining a diester from a carboxylic acid dianhydride and an alcohol, adding a diamine, and then adding a condensing agent such as dicyclohexylcarbodiimide to react at -30 ° C to room temperature for 1 to 8 hours; tetracarboxylic dianhydride Using a known method such as a method of obtaining a diester with a product and an alcohol, converting the remaining dicarboxylic acid into an acid chloride, adding a diamine, and reacting at −30 ° C. to room temperature for 1 to 8 hours. Can be. Examples of the reaction solvent used in these known methods include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ-butyrolactone, and the like.

R ³ and R ^{4 in the} general formulas (1) to (5) may be the same or different and are represented by hydrogen or the general formulas (6) to (7), each of which has 1 to 20 carbon atoms. Represents an alkyl group.

  α is an integer of 0 to 19, preferably 0 to 3. β is an integer of 0 to 16, preferably 0 to 2.

From the viewpoint of the stability of the obtained positive photosensitive resin solution, R ³ and R ⁴ are preferably alkyl groups, but hydrogen is preferable from the viewpoint of the solubility of the aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amounts of hydrogen and alkyl groups of R ³ and R ^4, the dissolution rate in an aqueous alkali solution changes, so that a positive photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. it can. The preferred range is that from 10% to 90% of the R ³ and R ⁴ are hydrogen atoms. When R ³ and R ^{4 have} more than 20 carbon atoms, they do not dissolve in an aqueous alkaline solution. From the above, it is preferable that R ³ and R ⁴ contain one or more hydrocarbon groups having 1 to 16 carbon atoms, and the others are hydrogen atoms.

—NH— (R ⁵ ) m—X, which is a structural component in the general formulas (2) and (3), is represented by the following general formula (8). It is a component derived from monoamine.

Also, it is the structural component of the general formula (4) and general formula (5) in -CO- (R ⁵⁾ m-Y is represented by the following general formula (9) and / or the following general formula (10), These are components derived from those selected from acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds, which are terminal blocking agents.

R ^{5 in the} general formulas (8) to (10) represents a divalent organic group, and is preferably —CR ¹¹ R ¹² —, —CH ² O—, or —CH ² SO ² —. R ¹¹ and R ¹² each represent a monovalent group selected from a hydrogen atom, a hydroxyl group, and a hydrocarbon group having 1 to 10 carbon atoms. R ⁹ and R ¹⁰ are a monovalent group selected from a hydrogen atom, a hydroxyl group, a carboxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a zero-valent group indicating that R ⁹ and R ¹⁰ are directly bonded. Show. R ⁸ represents a hydrogen atom or a monovalent group selected from hydrocarbon groups having 1 to 10 carbon atoms. Among them, a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, a methyl group and a t-butyl group are particularly preferable. R ⁶ and R ⁷ are a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a hydrocarbon group having at least one unsaturated hydrocarbon group having 1 to 10 carbon atoms, a nitro group, a methylol group. , An ester group, a hydroxyalkynyl group, or a hydrocarbon group having 1 to 10 carbon atoms. A ^{1 to} A ³ are each a carbon atom or a nitrogen atom. m is an integer from 0 to 10, preferably an integer from 0 to 4. l is 0 or 1, and preferably 0. i is 0 or 1, preferably 0. j is an integer from 1 to 3, preferably 1 and 2. k, t, and u are 0 or 1.

  The primary monoamine which is a terminal blocking agent represented by the general formula (8) includes 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy- 7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3 -Aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-ca Boxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-amino Naphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy -4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-amido Salicylic acid, 3-amino-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfone Acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto- 8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7 -Mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1 -Amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4- Ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-amino Naphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl- -Aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2 -Ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8- Aminonaphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7 -Diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthale , 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-amino-naphthalene, and the like, but it is not limited thereto.

  Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5- Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic , 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminophenol Preferred are aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline and the like.

  Compounds selected from acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds, which are terminal blocking agents represented by the general formulas (9) and (10), are phthalic anhydride and maleic anhydride. , Nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene , 1-hydroxy-3-ca Boxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1 -Mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynyl Benzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5 -Diethynylbenzoic acid, 2 Ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid Acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl Monocarboxylic acids such as -2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds in which the carboxyl groups thereof are acid chlorided; terephthalic acid, phthalic acid, Maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, , 3-Dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3 Monocarboxylic acid compounds in which only monocarboxylic groups of dicarboxylic acids such as dicarboxylic naphthalene, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene are acid chlorided, monoacid chloride compounds and N-hydroxybenzotriazole, Active ester compounds obtained by reaction with N-hydroxy-5-norbornene-2,3-dicarboximide.

  Among these, phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene , 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid Such as acid Carboxylic acids and monoacid chloride compounds in which the carboxyl groups thereof are acid chlorides, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- Monocarboxylic acid compounds in which only the monocarboxyl group of dicarboxylic acids such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid chlorided, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2 Active ester compounds obtained by reaction with 2,3-dicarboximide are preferred.

  The introduction ratio of the monoamine component represented by the general formula (8) is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on all amine components. The introduction ratio of the component selected from the acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds represented by the general formulas (9) and (10) is 0.1 to the diamine component. The range is preferably from 100 to 100 mol%, particularly preferably from 5 to 90 mol%. A plurality of different end groups may be introduced by reacting a plurality of end capping agents.

  N in the general formulas (1) to (5) indicates the number of repeating structural units of the polymer of the present invention, and is preferably in the range of 10 to 100,000.

Further, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized in R ¹ and R ² as long as the heat resistance is not reduced. Specific examples of the diamine component include those obtained by copolymerizing bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, etc. in an amount of 1 to 15 mol%.

  The polymers represented by the general formulas (1) to (5) of the present invention are obtained by substituting a part of the diamine with a terminal blocking agent which is a monoamine, or replacing the acid dianhydride with a monocarboxylic acid, an acid anhydride, It is synthesized by replacing the monoacid chloride compound and the terminal blocking agent which is a monoactive ester compound. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a terminal capping agent which is a monoamine) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially an acid anhydride or A method of reacting a monoacid chloride compound or a monoactive ester compound with a terminal blocking agent) and a diamine compound, obtaining a diester by tetracarboxylic dianhydride and an alcohol, and then diamine (partially a monoamine terminal compound) A method of reacting with a sealing agent) in the presence of a condensing agent, obtaining a diester by tetracarboxylic dianhydride and an alcohol, and then acid-chlorinating the remaining dicarboxylic acid, and diamine (a terminal part of which is a monoamine) (Replacement with a sealing agent).

  The terminal blocking agent introduced into the polymer can be easily detected by the following method. For example, a polymer having a terminal blocking agent introduced therein is dissolved in an acidic solution, decomposed into an amine component and an acid anhydride component, which are constituent units of the polymer, and the resulting component is subjected to gas chromatography (GC) or NMR measurement to obtain a polymer. The terminal blocking agent can be easily detected. Further, it is possible to directly measure a pyrolysis gas chromatograph (PGC), an infrared spectrum and a C13 NMR spectrum of the polymer component into which the terminal blocking agent has been introduced.

  The alkali-soluble resin used in the present invention comprises only a phenol resin, a polymer containing a radical polymerizable monomer having an alkali-soluble group, and each of the structural units represented by the general formulas (1) to (5). Or a polymer containing a phenolic resin, a radical polymerizable monomer having an alkali-soluble group, and at least one polymer selected from the structural units represented by general formulas (1) to (5). May be a copolymer or a blend. In the case of a copolymer or a blend, a phenol resin, a polymer containing a radical polymerizable monomer having an alkali-soluble group, and 50 mol% or more of each structural unit represented by the general formulas (1) to (5). It is preferable that it is contained. It is more preferably at least 70 mol%. The type and amount of the structural unit used for the copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.

  An epoxy compound and an epoxy curing agent may be added to the alkali-soluble resin used in the present invention. Examples of the epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolak epoxy compound, a cresol novolak epoxy compound, a trishydroxyphenylmethane type epoxy compound, an alicyclic epoxy compound, a glycidyl ester-based epoxy compound, and a glycidylamine-based epoxy compound. Epoxy compounds, heterocyclic epoxy compounds, fluorene group-containing epoxy compounds, and the like can be used. On the other hand, conventional curing agents such as alcohols, phenols, amines, acid anhydrides, carboxylic acids, and compounds having active hydrogen can be used. Further, a cationic curing catalyst such as an onium salt may be used.

  The quinonediazide compound (b) is preferably a compound having a phenolic hydroxyl group and a sulfonic acid of naphthoquinonediazide bonded by an ester. Compounds having a phenolic hydroxyl group include Bis-Z, BisP-EZ, TekP-TPA, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-PHBA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP- IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-p-CR, Methylenetetra-p-CR, BisRS-26X, Bis-PFP-PC (trade names, BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (manufactured by Honshu Chemical Industry Co., Ltd.) , Trade name, manufactured by Asahi Organic Materials Co., Ltd.), naphthol, tetrahi Compounds such as roxybenzophenone, gallic acid methyl ester, bisphenol A, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) are combined with 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid through an ester bond. Those introduced are preferred. Sulfonamide compounds in which naphthoquinonediazidosulfonic acid is bonded to a compound having an amino group can also be used. Compounds other than these can also be used.

  The structure of the compound having a phenolic hydroxyl group is shown below as a specific example.

  When the molecular weight of the naphthoquinonediazide compound used in the present invention exceeds 1,000, the naphthoquinonediazide compound does not thermally decompose sufficiently in the subsequent heat treatment, so that the heat resistance of the obtained film is reduced, the mechanical properties are reduced, There is a possibility that problems such as a decrease in performance may occur. Therefore, the molecular weight of the preferred naphthoquinonediazide compound is from 300 to 1,000. More preferably, it is 350 to 800. The addition amount of the naphthoquinonediazide compound is preferably 1 to 50 parts by weight based on 100 parts by weight of the polymer.

  If necessary, the compound having a phenolic hydroxyl group may be used without esterification with naphthoquinonediazide for the purpose of supplementing the alkali developability of the photosensitive precursor composition. When this compound having a phenolic hydroxyl group is added, the resin composition hardly dissolves in an alkali developing solution before exposure, and easily dissolves in an alkali developing solution upon exposure, so that the film loss due to development is small and short. Development becomes easier with time. In this case, the addition amount of the compound having a phenolic hydroxyl group is preferably from 1 to 50 parts by weight, more preferably from 3 to 40 parts by weight, based on 100 parts by weight of the polymer.

  The component (c) is a thermochromic compound that develops color upon heating and exhibits an absorption maximum at 350 nm or more and 700 nm or less, more preferably a thermochromic compound that develops color upon heating and exhibits an absorption maximum at 350 nm or more and 500 nm or less. In the case of a thermochromic compound in which the component (c) develops a color by heating to a wavelength lower than 350 nm or a wavelength longer than 700 nm and exhibits an absorption maximum, the compound does not absorb in the visible light wavelength region after the final heat treatment performed after pattern processing. It is difficult to blacken.

  The component (c) of the present invention is preferably a compound which forms a color at a temperature higher than 120 ° C, more preferably a compound which forms a color at a temperature higher than 180 ° C. The higher the coloring temperature of the thermochromic compound, the better the heat resistance under high temperature conditions, and the less the color fades due to the long-term ultraviolet-visible light irradiation, the better the light resistance.

  The component (c) of the present invention may be a general heat-sensitive dye or a pressure-sensitive dye, or may be another compound. These thermochromic compounds develop color by changing their chemical structure and charge state by the action of acidic groups coexisting in the system when heated, or cause thermal oxidation reactions etc. due to the presence of oxygen in the air. And the like that develop color. Examples of the skeleton structure of the thermochromic compound include a triarylmethane skeleton, a diarylmethane skeleton, a fluoran skeleton, a bislactone skeleton, a phthalide skeleton, a xanthene skeleton, a rhodamine lactam skeleton, a fluorene skeleton, a phenothiazine skeleton, a phenoxazine skeleton, and a spiropyran skeleton. Can be Specifically, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, 4,4 ′, 4 ″ -tris (diethylamino) -2,2 ′, 2 ″ -trimethyltriphenylmethane, 4 ′, 4 ″ -methylidene trisphenol, 4,4 ′, 4 ″ -methylidene trisphenol, 4,4 ′-[(4-hydroxyphenyl) methylene] bis (benzeneamine), 4,4 ′-[ (4-aminophenyl) methylene] bisphenol, 4,4 ′-[(4-aminophenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [ 2,3,6-trimethylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, 4,4 ′-[(2-hydroxyphenyl) methylene Bis [2-methylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4, 4 ′-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2 ′ -[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol], 2, 2 '-[(2-hydroxyphenyl) methylene] bis [2,3,5-trimethylphenol], 4,4'-[(4-hydroxyphenyl) methylene Bis [2,3,6-trimethylphenol], 4,4 '-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4'-[(3-hydroxyphenyl) Methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(3-methoxy -4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[ (3,4-dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) Methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,4 ′, 4 ″, 4 "'-(1,2-ethanediylidene) tetrakisphenol, 4,4', 4", 4 "'-(1,2-ethanediylidene) tetrakis [2-methylphenol], 4,4', 4", 4 "'-(1,2-ethanediylidene) tetrakis [2,6-dimethylphenol], 4,4', 4", 4 "'-(1,4-phenylenedimethylidene) tetrakisphenol, 4,4', 4 ", 4" '-(1,4-phenylenedimethylidene) tetrakis (2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl) methylene] bis [3-methylphenol , 2,2 '-[(3-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,5-dimethyl Phenol], 4,4 '-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(2-hydroxy-3-methoxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene ] Bis [2-methylethylphenol], 4,4 '-[(3-hydroxyphenyl) methylene] bis [2-methylethylphenol], 4,4'-[(4- (Droxyphenyl) methylene] bis [2-methylethylphenol], 2,2 ′-[(3-hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4- (Hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4′- [(2-hydroxy-3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 4,4 '-[(3-hydroxy-4-methoxyphenyl) methylene] bis [2- (methylethyl) Phenol], 4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2'-[(2- Hydroxy-3-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol] , 2,2 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4'-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy -3-ethoxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] [2- (1,1-dimethylethyl) -5-methylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(3- (Hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(2-hydroxy-3-methoxyphenyl) ) Methylene] bis [2-cyclohexylphenol], 4,4 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxy-3- Ethoxyphenyl) methylene] bis [2- (1,1-dimethylethyl) -6-methylphenol], 4,4 ′-[(4-hydrogen [Xy-3-ethoxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ', 4 "-methylidenetris [2-cyclohexyl-5-methylphenol], 2,2'-[(3, 4-dihydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[ (3,4-dihydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2-cyclohexylphenol], 3,3 ′ -[(2-hydroxyphenyl) methylene] bis [5-methylbenzene-1,2-diol], 4,4 '-[4-[[bis (4-hydrido Roxy-2,5-dimethylphenyl) methyl] phenyl] methylene] bis [1,3-benzenediol], 4,4′-methylenebis [2- [di (4-hydroxy-3-methylphenyl)] methyl] phenol 4,4'-methylenebis [2- [di (4-hydroxy-2,5-dimethylphenyl)] methyl] phenol, 4,4'-methylenebis [2- [di (4-hydroxy-3,5-dimethyl) Phenyl)] methyl] phenol, 4,4′-methylenebis [2- [di (3-cyclohexyl-4-hydroxy-6-methylphenyl)] methyl] phenol, 4,4 ′-(3,5-dimethyl-4) -Hydroxyphenylmethylene) -bis (2,6-dimethylphenol), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 3,6-bis (dimethylamino) fluoran-γ- (4′-nitro) -aminolactam, 2- (2-chloroanilino) -6-diethylaminofluoran, 2- (2-chloroanilino) -6-dibutylaminofuran Oran, 2-N, N-dibenzylamino-6-diethylaminofluoran, 6-diethylamino-benzo [a] -fluoran, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 ′ -Tetraphenyl-1,2'-bi (imidazole), 1,3-dimethyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-dibutylaminofluoran, 3,7-bis (dimethylamino) -10-benzoylphenothiazine, 3-diethylamino-6-chloro-7- (β-ethoxyethylamino) fluoran, 3-diethylamido 6-methyl-7-anilinofluoran, 3-triethyl-6-methyl-7-anilinofluoran, 3-cyclohexylamino-6-methyl-7-anilinofluoran, and the like.

  Among these, a hydroxyl group-containing compound having a triarylmethane skeleton represented by the general formulas (11) and (12) is preferable.

R ^{13 to} R ²⁸ may be the same or different, and include a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a cyclic aliphatic group having 3 to 8 carbon atoms, and an aromatic ring having 6 to 15 carbon atoms. And a monovalent group selected from an alkoxy group having 1 to 4 carbon atoms. l is 0 or 1, and preferably 0. γ is an integer of 0 to 3, preferably 1. W1 to W23 are integers from 0 to 4. W1 + W2 + W3> 0 and W10 + W11 + W12 + W13> 0.

  Specifically, 2,4 ′, 4 ″ -methylidene trisphenol, 4,4 ′, 4 ″ -methylidene trisphenol, 4,4 ′-[(4-hydroxyphenyl) methylene] bis (benzeneamine), 4,4 ′-[(4-aminophenyl) methylene] bisphenol, 4,4 ′-[(4-aminophenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxy Phenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [ 2-methylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4- [bis (4-hydroxyphenyl) methyl ] -2-ethoxyphenol, 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(4-hydroxyphenyl) methylene] bis [3,5 -Dimethylphenol], 4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(2-hydroxyphenyl) methylene] bis [2 , 3,5-trimethylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4'-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol ], 4,4 '-[(3-methoxy-4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4'-[(3,4-dihydroxyphenyl) methylene] bis [ 2-methylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4'-[(3,4-dihydroxyphenyl) methylene] bis [ 2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,4 ′, 4 ″, 4 ″ ′- (1,2-ethanediylidene) tetrakisphenol, 4,4 ′, 4 ″, 4 ″ ′-(1,2-ethanediylidene) tetrakis [2-methylphenol], 4,4 ′, 4 ″ , 4 "'-(1,2-ethanediylidene) tetrakis [2,6-dimethylphenol], 4,4', 4", 4 "'-(1,4-phenylenedimethylidene) tetrakisphenol, 4,4' , 4 ", 4" '-(1,4-phenylenedimethylidene) tetrakis (2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4 , 4 '-[(2-Hydroxy-3-methoxyphenyl) methylene] bis [2,5-dimethylphenol], 4,4'-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,6 -Dimethylphenol], 2,2 '-[(2-hydroxy-3-methoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(2-hydroxyphenyl ) Methylene] bis [2-methylethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-methylethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxy- 3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 4,4 ′-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 '-[(2-hydroxy-3-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2'-[(4-hydroxy-3-meth [Xyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2′- [(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2,3,6 -Trimethylphenol], 4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2- (1,1-dimethylethyl) -5-methylphenol], 4,4'-[(2 -Hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexylphenol ], 4,4 '-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4'-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2 -(1,1-dimethylethyl) -6-methylphenol], 4,4 '-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4' , 4 "-methylidenetris [2-cyclohexyl-5-methylphenol], 2,2 '-[(3,4-dihydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(3 , 4-Dihydroxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 '-[(3,4-dihydroxyphenyl) methylene] bis [3 5,6-trimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2-cyclohexylphenol], 3,3 ′-[(2-hydroxyphenyl) methylene] bis [5- Methylbenzene-1,2-diol], 4,4 '-[4-[[bis (4-hydroxy-2,5-dimethylphenyl) methyl] phenyl] methylene] bis [1,3-benzenediol], 4 4,4'-Methylenebis [2- [di (4-hydroxy-3-methylphenyl)] methyl] phenol, 4,4'-methylenebis [2- [di (4-hydroxy-2,5-dimethylphenyl)] methyl ] Phenol, 4,4'-methylenebis [2- [di (4-hydroxy-3,5-dimethylphenyl)] methyl] phenol, 4,4'-methylenebis [2- Di (3-cyclohexyl-4-hydroxy-6-methylphenyl)] methyl] phenol and 4,4 ′-(3,5-dimethyl-4-hydroxyphenylmethylene) -bis (2,6-dimethylphenol) Hydroxyl group-containing compounds having a triarylmethane skeleton are particularly preferred because of their high thermal coloring temperature and excellent heat resistance. These may be used alone or as a mixture. The hydroxyl group-containing compound having a triarylmethane skeleton may be used as a quinonediazide compound by subjecting the compound to a sulfonic acid of naphthoquinonediazide through an ester bond.

  The amount of the thermochromic compound (c) used in the present invention is preferably from 1 to 300 parts by weight, particularly preferably from 10 to 200 parts by weight, per 100 parts by weight of the alkali-soluble resin (a). When the amount of the thermochromic compound (c) used is more than 300 parts by weight per 100 parts by weight of the alkali-soluble resin (a), the resin ratio decreases, and the adhesion strength between the photosensitive resin film and the substrate decreases.

  The component (d) of the present invention is a compound having no absorption maximum at 350 nm or more and less than 500 nm but having an absorption maximum at 500 nm or more and 750 nm or less. The compound preferably uses a dye and / or an organic pigment. The component (d) may be at least one kind, for example, a method using one kind of dye or organic pigment, a method using two or more kinds of dyes or organic pigments mixed, one kind of dye or one kind or more. In the present invention, a method having an absorption maximum at 500 to 750 nm is preferably selected.

  The dye used as the component (d) is preferably a dye which is soluble in the organic solvent capable of dissolving the alkali-soluble resin (a) and is compatible with the resin. Preferred dyes include, for example, oil-soluble dyes, disperse dyes, reactive dyes, acid dyes and direct dyes. As the skeleton structure of the dye, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, and metal-containing complex salts of these dyes can be used, among which phthalocyanine-based and metal-containing complex-based ones can be used. Excellent in heat resistance and light resistance, and more preferable. Specifically, Sumilan, Lanyl dye (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, Irgasperse dye (manufactured by Ciba Specialty Chemicals Co., Ltd.) Zapon, Neozapon, Neptune, Acidol dye (BASF (manufactured by BASF) Kayaset, Kayakalan dyes (Nippon Kayaku Co., Ltd.), Balifast colors dyes (Orient Chemical Co., Ltd.) Savinyl, Sandoplast, Polysynthren, Lanasyn dyes (Clariant Japan Co., Ltd.), Aizen Spilon dye ( Hodogaya Chemical Industry Co., Ltd.). These dyes are used alone or in combination.

  As the organic pigment used as the compound of the component (d) of the present invention, a pigment having high heat resistance and light resistance is preferable.

  Specific examples of the organic pigment used in the present invention are shown by color index (CI) numbers. Examples of purple pigments include Pigment Violet 19, 23, 29, 32, 33, 36, 37, 38 and the like. Examples of blue pigments include Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64 and the like. Examples of green pigments include Pigment Green 7, 10, 36, 47, and the like. Pigments other than these can also be used.

  The amount of the compound (d) used in the present invention is preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a). If the amount of the compound (d) is more than 300 parts by weight based on 100 parts by weight of the alkali-soluble resin (a), the resin ratio decreases, and the adhesion strength between the photosensitive resin film and the substrate decreases.

  In the present invention, as the organic pigment, a pigment having been subjected to a surface treatment such as a rosin treatment, an acidic group treatment, or a basic group treatment may be used, if necessary. In addition, it can be used together with a dispersant in some cases. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants.

  In order to apply the photosensitive composition of the present invention on a substrate, the above-described components are dissolved or dispersed in a solvent to prepare a liquid composition (varnish). Preferred examples of the solvent used include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ-butyrolactone, N-methyl-2-pyrrolidone, Examples of the organic solvent that dissolves the alkali-soluble resin as the component (a) of the present invention, such as methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutanol, ethyl lactate, and diacetone alcohol. However, it is not limited to this. The organic solvents may be used alone or in combination of two or more. The solid content concentration in the varnish is not particularly limited, but is usually about 5 to 50% by weight, preferably about 10 to 40% by weight based on the total amount of the composition.

  Further, if necessary, a surfactant, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, or a surfactant is used for the purpose of improving the wettability between the positive photosensitive resin composition and the substrate. Mixing esters such as -methyl-3-methoxybutyl acetate, alcohols such as 3-methyl-2-butanol and 3-methyl-3-methoxybutanol, ketones such as cyclohexanone, and ethers such as tetrahydrofuran and dioxane. May be used. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or powder of polyimide can also be added.

Further, in order to enhance the adhesion to a silicon wafer, an ITO substrate, or an underlying substrate such as SiO ₂ , a silane coupling agent, a titanium chelating agent, or the like is added to the varnish of the photosensitive resin composition in an amount of 0.005 to 10% by weight. Alternatively, the underlying substrate can be pre-treated with such a chemical solution.

  When added to the varnish, 0.005 to 10% by weight of a silane coupling agent such as methylmethacryloxydimethoxysilane, 3-aminopropyltrimethoxysilane, a titanium chelating agent, or an aluminum chelating agent is added to the polymer in the varnish. I do.

  When treating the substrate, the coupling agent described above is mixed with a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate for 0.5 to 20 minutes. The solution in which the weight% is dissolved is subjected to a surface treatment by spin coating, slit die coating, bar coating, dip coating, spray coating, steam treatment or the like. In some cases, the reaction between the substrate and the coupling agent proceeds by applying a temperature of 50 ° C. to 300 ° C. in some cases.

  Next, a method for forming a heat-resistant resin pattern using the photosensitive resin composition of the present invention will be described.

  The photosensitive resin composition is applied on a substrate. Examples of the material of the substrate include, for example, metals, glasses, semiconductors, metal oxide insulating films, silicon nitride, polymer films, and any other materials on the surface of which a metal for an electrode can be provided. Preferably, glass is used. Although there is no particular limitation on the material of the glass, alkali zinc borosilicate glass, sodium borosilicate glass, soda lime glass, low alkali borosilicate glass, barium borosilicate glass, borosilicate glass, aluminosilicate glass, molten Quartz glass, synthetic quartz glass, or the like is used. Usually, alkali-free glass or soda-lime glass coated with a barrier coat such as SiO2, which has a small amount of ions eluted from the glass, is used. The thickness is 0.1 mm or more, preferably 0.5 mm or more, as long as it is sufficient to maintain the mechanical strength. The coating method includes a slit die coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method, and the like. The coating may be performed by combining these methods, but the photosensitive resin composition of the present invention may be used. The most effective is the slit die coating method. The coating thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 100 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying uses a hot plate, an oven, infrared rays, a vacuum chamber, and the like.

When a hot plate is used, the object to be heated is held directly on the plate, or the object to be heated is held on a jig such as a proxy pin installed on the plate and heated. Examples of the material of the proxy pin include a metal material such as aluminum and stainless steel, and a synthetic resin such as a polyimide resin and Teflon (registered trademark). A proxy pin of any material may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the resin layer to be heated, the purpose of heating, and the like. For example, the resin layer applied on a 300 × 350 × 0.7 mm ³ glass substrate When heating, the height of the proxy pin is preferably about 2 to 12 mm.

  The heating temperature varies depending on the type and purpose of the object to be heated, and it is preferable to perform the heating in the range of room temperature to 180 ° C. for 1 minute to several hours.

  Next, the photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern to expose the photosensitive resin composition film. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. .

  The formation of the heat-resistant resin pattern is achieved by removing the exposed portion using a developer after exposure. The developing solution is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino. An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred. The pH range of the developer is usually adjusted to 10 or more and 14 or less. In addition, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol, etc. Alcohols, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination of several kinds. After development, it is rinsed with water. Here, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

  After development, the film is converted into a heat-resistant resin film by applying a temperature of 130 ° C. to 350 ° C. in an air or nitrogen atmosphere. The heat treatment atmosphere particularly suitable for the photosensitive resin composition of the present invention is an air atmosphere. In a heat treatment in an air atmosphere, an oxidation reaction occurs due to the presence of oxygen, and the oxidation reaction often promotes the coloring of the thermochromic compound. This heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise or while selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method in which the temperature is linearly raised from room temperature to 250 ° C. over 2 hours or from 350 ° C. over 2 hours may be used.

  The optical density (OD value) at a thickness of 1.0 μm of the heat-resistant resin film obtained by heat-treating the photosensitive resin composition of the present invention is preferably 0.3 or more. More preferably, it is 0.5 or more. When the optical density is smaller than 0.3, the contrast between the light emitting area and the non-light emitting area of the display manufactured using the same is not improved. Therefore, it is difficult to obtain a function as a light-shielding separator or a black matrix of an organic electroluminescent device or a liquid crystal display device.

The heat-resistant resin film obtained by heat-treating the photosensitive resin composition of the present invention has an optical density retention of 50% or more after irradiation with light using a xenon fade meter for 500 hours before irradiation. The resin coating formed by using only the thermochromic compound (c) has an optical density retention of less than 50%. In this case, the light resistance becomes insufficient, and the optical density of the insulating layer decreases from its initial optical density over a long period of use. It is difficult to obtain a function as a light-shielding separator or a black matrix. Therefore, the retention of the optical density is preferably 50% or more, more preferably 70% or more, and particularly preferably 90% or more. In the present invention, the optical density is determined under the following conditions. The coating is irradiated for 500 hours through a polarizing filter with a transmittance of 45% at an illuminance of 72,000 lux under a xenon arc lamp light source. The optical densities before and after the irradiation were set to O.D. D ₁ , O.D. And D _2, was determined by the following equation of the optical density retention rate as r.
r (%) = O. D ₂ / O. D ₁ × 100
In the present invention, as shown in FIG. 1, the cross section of the insulating layer 3 at the exposed boundary of the first electrode 4 formed on the substrate 5 preferably has a forward tapered shape. Here, the tapered shape indicates that the angle θ in the drawing is less than 90 °. The cross-sectional shape of the insulating layer is preferably 60 ° or less, more preferably 45 ° or less, and further preferably 30 ° or less. If the cross-sectional shape is larger than 60 °, the thin film layer 2 and the second electrode 1 tend to be thinner at the boundary between the insulating layers, and luminance unevenness tends to occur in the light emitting region. In addition, as the driving time increases, moisture or a small amount of gas enters from the interface between the insulating layer and the second electrode, which easily causes the dark area to expand. In addition, electric field concentration is likely to occur at the edge portion of the electrode, and undesirable phenomena such as dielectric breakdown and generation of leak current are likely to occur.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The evaluation of the optical density, the evaluation of light resistance, the cross-sectional shape, and the evaluation of the light emission characteristics in the examples were performed by the following methods.
(1) Evaluation of Optical Density The optical density (OD) was measured using a microspectroscope (“MCPD2000” manufactured by Otsuka Electronics Co., Ltd.), the incident light intensity in the visible region of wavelength 430 to 640 nm was I0, and the transmitted light intensity was And I was determined by the following equation.

O. D = log10 (I0 / I)
(2) Evaluation of light resistance The heat-resistant resin film formed on the alkali-free glass by the heat treatment was measured using a xenon long life fade meter (manufactured by Suga Test Instruments Co., Ltd.) under a xenon arc lamp light source of 72,000. The optical density before and after holding for 500 hours through a polarizing filter having a transmittance of 45% at an illuminance of O. D1, O.D. D2 and the optical density retention rate as r were determined by the following equation.
r (%) = O. D2 / O. D1 × 100
(3) Evaluation of cross-sectional shape The cross-sectional shape of a 20 μm pattern line of the heat-resistant resin film obtained by the heat treatment was observed using a scanning electron microscope (“S-4800”, manufactured by Hitachi, Ltd.). 1 was measured in FIG.
(4) Evaluation of durability of light emission A simple matrix type organic electroluminescent display device was manufactured, the effective light emitting area was S1, and the light emitting area after a durability test at 85% humidity for 250 hours was S2. The effective light emitting area ratio after the test was determined as S by the following equation.

S (%) = (S2 / S1) × 100
Synthesis Example 1 Synthesis of Hydroxy Group-Containing Acid Anhydride (A) Under a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl 34.2 g (0.3 mol) of glycidyl ether was dissolved in 100 g of gamma-butyrolactone and cooled to -15C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After the completion of the dropwise addition, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator, and then added to 1 liter of toluene to obtain an acid anhydride (A).

Synthesis Example 2 Synthesis of Hydroxy Group-Containing Diamine Compound (B) 15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 50 ml of acetone and 30 g (0.34 mol) of propylene oxide. Cool. A solution in which 17.8 g (0.055 mol) of 2,2-bis (4-benzoyl chloride) propane was dissolved in 60 ml of acetone was gradually added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration.

This precipitate was dissolved in 200 ml of γ-butyrolactone, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued at room temperature until the hydrogen gas balloon did not shrink any more, and further stirred for 2 hours with the hydrogen gas balloon attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to a half volume with a rotary evaporator. Ethanol was added thereto and recrystallization was performed to obtain crystals of the target compound.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine compound (C) 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution of 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride dissolved in 100 ml of acetone was added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at −15 ° C. for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and dried at 50 ° C. in vacuo.

  30 g of the obtained solid was placed in a 300 ml stainless steel autoclave, dispersed in 250 ml of methylcellosolve, and 2 g of 5% palladium-carbon was added. Here, hydrogen was introduced by a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon did not deflate any more, and the reaction was terminated. After completion of the reaction, the mixture was filtered to remove the palladium compound as a catalyst, and concentrated by a rotary evaporator to obtain a diamine compound (C). The obtained solid was used for the reaction.

Synthesis Example 4 Synthesis of Hydroxy Group-Containing Diamine Compound (D) 15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide to give -15. Cooled to ° C. A solution of 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride dissolved in 100 ml of acetone was gradually added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration. Thereafter, a crystal of the target compound was obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride solution (E) 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride under a stream of dry nitrogen 24.82 g (0.08 mol) of the product and 59.3 g (0.8 mol) of n-butyl alcohol were reacted with stirring at 95 ° C. for 6 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester. Then, 95.17 g (0.8 mol) of thionyl chloride and 70 g of tetrahydrofuran (THF) were charged and reacted at 40 ° C. for 3 hours. Subsequently, 200 g of N-methylpyrrolidone was added, excess thionyl chloride and THF were removed under reduced pressure, and 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride solution (E) 239 was obtained. 0.6 g (0.08 mol) were obtained.

Synthesis Example 6 Synthesis of quinonediazide compound (F) Under dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 33.58 g of 5-naphthoquinonediazidosulfonyl chloride (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the reaction system did not become 35 ° C. or higher. After the dropwise addition, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum drier to obtain a quinonediazide compound (F).

Synthesis Example 7 Synthesis of quinonediazide compound (G) Under dry nitrogen stream, 6.81 g (0.05 mol) of 4-isopropylphenol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidosulfonyl chloride were mixed with 1,4-methylphenol. It was dissolved in 450 g of dioxane and brought to room temperature. Here, quinonediazide compound (G) was obtained in the same manner as in Synthesis Example 6 using 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 8 Synthesis of quinonediazide compound (H) Under dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 5-naphthoquinonediazidosulfonyl chloride were mixed with 450 g of 1,4-dioxane. And brought to room temperature. Here, quinonediazide compound (H) was obtained in the same manner as in Synthesis Example 6 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 9 Synthesis of active ester compound (I) Under dry nitrogen stream, 18.5 g (0.1 mol) of 4-carboxybenzoic acid chloride and 13.5 g (0.1 mol) of hydroxybenzotriazole were added to 100 g of tetrahydrofuran (THF). And cooled to -15 ° C. To this, 10 g (0.1 mol) of triethylamine dissolved in 50 g of THF was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After the completion of the dropwise addition, the reaction was carried out at 25 ° C. for 4 hours. This solution was concentrated using a rotary evaporator to obtain an active ester compound (I).

Synthesis Example 10 Synthesis of alkali-soluble polymer (J) 9.61 g (0.016 mol) of hydroxyl-containing acid anhydride (A) was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP) under a stream of dry nitrogen. To this, 12 g (0.02 mol) of the hydroxyl group-containing diamine (B) was added together with 25 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. Next, 0.78 g (0.008 mol) of maleic anhydride was added as a terminal blocking agent, and the mixture was reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 40 hours to obtain an alkali-soluble polymer (J).

Synthesis Example 11 Synthesis of alkali-soluble polymer (K) Under a dry nitrogen stream, 12.01 g (0.02 mol) of a hydroxyl group-containing acid anhydride (A) was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). To this, 4.84 g (0.008 mol) of the hydroxyl-containing diamine (C) and 1.94 g (0.008 mol) of the hydroxyl-containing diamine (D) were added together with 25 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. For 2 hours. Next, 0.94 g (0.008 mol) of 4-ethynylaniline was added and reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 40 hours to obtain an alkali-soluble polymer (K).

Synthesis Example 12 Synthesis of alkali-soluble polymer (L) Under a dry nitrogen stream, 9.67 (0.016 mol) of hydroxyl-containing diamine compound (C), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 86 g (0.0075 mol) and 0.94 g (0.008 mol) of 4-ethynylaniline as a terminal blocking agent were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 4 hours. Thereafter, a solution prepared by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried with a vacuum dryer at 70 ° C. for 60 hours to obtain an alkali-soluble polymer (L).

Synthesis Example 13 Synthesis of alkali-soluble polymer (M) 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added to N-methyl-2-pyrrolidone (NMP) under a stream of dry nitrogen. Dissolved in 50 g. To this, 1.09 g (0.01 mol) of 3-aminophenol was added as a terminal blocking agent, and the mixture was reacted at 40 ° C. for 1 hour. Next, 4.23 g (0.007 mol) of the hydroxyl group-containing diamine compound (c) and 0.6 g (0.003 mol) of 4,4′-diaminodiphenyl ether were added to 10 g of NMP, and the mixture was further reacted at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 5.96 g (0.05 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried with a vacuum dryer at 70 ° C. for 60 hours to obtain an alkali-soluble polymer (M).

Synthesis Example 14 Synthesis of alkali-soluble polymer (N) 18.68 g (0.051 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis ( 1.86 g (0.0075 mol) of 3-aminopropyl) tetramethyldisiloxane and 9.93 g (0.034 mol) of active ester compound (I) as a terminal blocking agent 11.93 g (0.151 mol) of pyridine were used. It was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 239.6 g (0.08 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride solution (e) was added dropwise so that the temperature inside the reaction system did not become 10 ° C. or more. did. After the addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 l of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain an alkali-soluble polymer (N).

Synthesis Example 15 Synthesis of alkali-soluble polymer (P) 7.75 g (0.051 mol) of 3,5-diaminobenzoic acid, 4 g (0.02 mol) of 4,4′-diaminodiphenyl ether under a dry nitrogen stream, end-blocking 1.96 g (0.018 mol) of 3-aminophenol and 12.66 g (0.16 mol) of pyridine were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP) as a stopper. Here, 239.6 g (0.08 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride solution (E) was added dropwise so that the temperature inside the reaction system did not become 10 ° C. or more. did. After the addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 l of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain an alkali-soluble polymer (P).

Example 1
57 g (0.6 mol) of meta-cresol, 38 g (0.4 mol) of para-cresol, 75.5 g (0.93 mol of formaldehyde) of a 37% by weight aqueous formaldehyde solution, 0.63 g (0.005 mol) of oxasan dihydrate Was dissolved in 264 g of methyl isobutyl ketone, and polycondensation was carried out for 4 hours with stirring while refluxing the reaction solution. Then, the temperature was raised over 3 hours. Thereafter, the pressure in the flask was reduced to 4000 to 6666 Pa to remove volatile components, and the molten resin was cooled to room temperature and collected. After dissolving this resin in ethyl acetate so that the resin component became 30%, 1.3 times as much methanol as the solution weight and 0.9 times as much water were added, and the mixture was stirred and left. Then, the lower layer separated into two layers was taken out, concentrated and dried to obtain a novolak resin.

  To 100 parts by weight of the novolak resin, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide- 30 parts by weight of a condensate with 5-sulfonic acid chloride (2 mol), 25 parts by weight of a thermochromic compound 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane (absorption maximum 600 nm), (d) 35 parts by weight of Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum at 670 nm), 2 parts by weight of a urethane dispersant (trade name: Disperbyk-182), and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane are mixed. And dissolved in propylene glycol monomethyl ether acetate to a solid concentration of 25% by weight. A varnish A1 of a resin composition was obtained.

A 300 × 350 mm glass substrate having a 130 nm thick ITO transparent electrode film formed on a 300 × 350 × 0.7 mm ³ alkali-free glass (Corning Japan Co., Ltd., # 1737) surface by a sputtering deposition method was prepared. . A photoresist was spin-coated on the ITO substrate and patterned by exposure and development using a normal photolithography method. After removing unnecessary portions of the ITO by etching, the photoresist was removed to pattern the ITO film into a stripe shape having a length of 90 mm and a width of 80 μm. This stripe-shaped first electrode has a pitch of 100 μm.

  A varnish A1 was applied to the ITO-patterned glass substrate by a slit die coating method so that the film thickness after soft baking became 1.5 μm. The coating speed was 3 m / min. When the spin coating method was used, coating was performed by adjusting the number of revolutions so that the film thickness after soft baking was 1.5 μm. Then, using a hot plate (EA-4331, manufactured by Chuo Riken Co., Ltd.), the glass substrate is held at a height of 5 mm from the hot plate with a proxy pin and heated at 90 ° C. for 3 minutes to apply a positive photosensitive resin. A membrane was obtained. The coating film of the varnish A1 was exposed to UV through a photomask, developed by dissolving only the exposed portion with a 2.38% aqueous solution of TMAH (tetramethylammonium), and rinsed with pure water. The obtained resin pattern was cured by heating at 220 ° C. for 60 minutes in an air atmosphere in a clean oven, and an insulating layer was formed so as to cover the edge of the first electrode. The thickness of the insulating layer was about 1 μm. A light-shielding insulating layer made of a photosensitive novolak resin was formed so that the center of the first electrode was exposed through an opening having a width of 70 μm and a length of 250 μm, and the end of the first electrode was covered. O. of the insulating layer D was 0.5. The cross section of the boundary portion of the insulating layer had a forward tapered shape as shown in FIG. 1, and the taper angle θ was about 60 °.

  Similarly, a light-shielding insulating layer was formed on non-alkali glass, and the light resistance was evaluated. As a result, the optical density retention ratio r was 60%.

  Next, an organic electroluminescent device was manufactured using the substrate on which the insulating layer was formed. The thin film layer including the light emitting layer was formed by a vacuum evaporation method using a resistance wire heating method. A hole transport layer was formed by vapor deposition over the entire effective area of the substrate, and a light emitting layer and aluminum as a second electrode were formed using a shadow mask.

  The obtained substrate was taken out of the vapor deposition machine, and the substrate and a glass plate for sealing were bonded and sealed with an ultraviolet-curable epoxy resin. A simple matrix type color organic electroluminescent device in which a patterned light emitting layer was formed on an ITO striped first electrode and a striped second electrode was arranged so as to be orthogonal to the first electrode was manufactured. When this display device was driven line-sequentially, good display characteristics could be obtained. The thin film layer and the second electrode were formed smoothly at the boundary portions of the insulating layer without being thinned or stepped. No luminance unevenness was observed in the light emitting region, and stable light emission was obtained. The effective light emission area ratio S after the durability test was 70%.

Example 2
176 g (0.1 mol) of t-butoxystyrene and 5.8 g (0.04 mol) of azobisisobutyronitrile were added to 250 ml of propylene glycol monomethyl ether, dissolved, and reacted at 75 ° C. for 4 hours. 50 g of a 5% by weight aqueous sulfuric acid solution was mixed with the obtained poly-t-butoxystyrene solution, and a hydrolysis reaction was performed at 100 ° C. for 3 hours. The reaction product was washed three times with 1000 ml of deionized water, and 500 ml of propylene glycol monomethyl ether acetate was added to perform solvent replacement to obtain an alkali-soluble resin (polyhydroxystyrene) solution.

  This alkali-soluble resin solution (corresponding to 100 parts by weight of polyhydroxystyrene (solid content)), 30 parts by weight of a quinonediazide compound (H), and 4,4 ′, 4 ″, 4 ″ ′-(1, 25 parts by weight of 4-phenylenedimethylidene) tetrakisphenol (absorption maximum 440 nm), 30 parts by weight of Pigment Blue 60 (indanthrone blue, absorption maximum of 570 nm, 720 nm), and Pigment Violet 19 (quinacridone red, absorption maximum of 510 nm, 550 nm, 600 nm) ) 10 parts by weight and 100 parts by weight of glass beads were mixed, dissolved in propylene glycol monomethyl ether acetate so as to have a solid concentration of 25% by weight, and dispersed with a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were filtered. Removed by positive type To obtain a varnish B1 of radiation-sensitive resin composition.

  The varnish B1 was applied on the substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 3 minutes to form a 2.2 μm-thick coating film. Evaluation was performed in the same manner as in Example 1 except that heating was performed at 220 ° C. for 60 minutes in an air atmosphere in a clean oven, and a display panel was manufactured.

Example 3
In a solution of 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 200 parts by weight of propylene glycol monomethyl ether acetate, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of methacrylic acid, After 45 parts by weight of glycidyl methacrylate and 25 parts by weight of dicyclopentanyl methacrylate were charged and replaced with nitrogen, the mixture was gently stirred. The temperature of the solution was maintained for 5 hours to obtain an acrylic resin solution.

  This acrylic resin solution (corresponding to 100 parts by weight of acrylic resin (solid content)), 25 parts by weight of a quinonediazide compound (G), and 4,4 ′, 4 ″ -methylidene trisphenol, a thermochromic compound (absorption maximum 460 nm) ) 25 parts by weight, 25 parts by weight of pigment blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm), 15 parts by weight of pigment blue 60 (indanthrone blue, absorption maximum 570 nm, 720 nm), urethane-based dispersant ( 2 parts by weight (trade name: Disperbyk-182) and 100 parts by weight of glass beads are mixed, dissolved in propylene glycol monomethyl ether acetate so as to have a solid concentration of 25% by weight, and subjected to a dispersion treatment at 7000 rpm for 30 minutes using a homogenizer. Then, the glass beads are removed by filtration, To obtain a varnish C1 type radiation-sensitive resin composition. Using this varnish C1, it was prepared display panel evaluated in the same manner as in Example 1.

Example 4
36 g of γ-butyrolactone was added to 2.5 g of Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum at 670 nm) and 1.5 g of Pigment Blue 60 (indanthrone blue, absorption maximum at 570 nm, 720 nm) as the component (d). Using a homogenizer together with 50 g of glass beads, a dispersion treatment was performed at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration to obtain an organic pigment dispersion having a concentration of 10% by weight. To 32 g of the dispersion, 5 g of an alkali-soluble polymer (J), 1.25 g of a thermochromic compound 4,4 ', 4 "-tris (dimethylamino) triphenylmethane (absorption maximum 600 nm), 2 g of a quinonediazide compound (H), and lactic acid A mixed solution of 9.75 g of ethyl was added to obtain a varnish D1 of a positive photosensitive resin composition.

  The substrate was coated with the varnish D1 by the slit die coating method and prebaked on a hot plate at 120 ° C. for 5 minutes to form a coating film having a thickness of 1.5 μm. Thereafter, evaluation was performed in the same manner as in Example 1 except that curing was performed at 250 ° C. for 30 minutes in an air atmosphere in a clean oven, and a display device was manufactured.

Example 5
To 2 g of Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum at 670 nm) as a component (d), 10 g of an alkali-soluble polymer (K), 37 g of γ-butyrolactone, and 44 g of 3-methyl-3-methoxybutyl acetate were added. Using a homogenizer together with 50 g of the beads, a dispersion treatment was performed at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration. 3 g of the quinonediazide compound (H) and 4 g of the thermochromic compound 4- [bis (4-hydroxyphenyl) methyl] 2-methoxyphenol (maximum absorption 470 nm) were added thereto, and the varnish of the positive photosensitive resin composition was added. E1 was obtained. Evaluation was performed in the same manner as in Example 4 except that the varnish E1 was used, and a display device was prepared.

Example 6
10 g of an alkali-soluble polymer (L), 2.2 g of a quinonediazide compound (F), 2.4 g of 4,4 ', 4 "-methylidene trisphenol (a maximum absorption of 460 nm) of a thermochromic compound, and 0.05 g of vinylmethoxysilane In addition to a mixed solvent of 39.95 g of γ-butyrolactone and 40 g of ethyl lactate, 3.0 g of azochrome complex salt-based dye (Varifast Black 1807 (absorption maximum: 580 nm)) and phthalocyanine-based dye (Varifast blue 2626 (maximum absorption: 680 nm)) are used as component (d). 2.4 g (manufactured by Orient Chemical Industry Co., Ltd., described in 2002.2 catalog) was added to obtain a varnish F1 of a positive photosensitive resin composition, and the varnish F1 was cured under a clean oven in an air atmosphere. Example 4 except for heating at 230 ° C. for 30 minutes under It has created a display device evaluated as.

Example 7
5 g of Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm) and 5 g of Pigment Blue 60 (indanthrone blue, absorption maximum 570 nm, 720 nm) as components (d), 20 g of alkali-soluble polymer (M), N- 50 g of methyl-2-pyrrolidone and 110 g of 3-methyl-3-methoxybutyl acetate were dispersed together with 100 g of glass beads at 7000 rpm for 30 minutes using a homogenizer, and then the glass beads were removed by filtration. To this, 7 g of the quinonediazide compound (H) and 3 g of 4,4 ′, 4 ″ -methylidene trisphenol (absorption maximum 460 nm) which is a thermochromic compound were added to obtain a varnish G1 of a positive photosensitive resin composition. Using the varnish G1, evaluation was performed in the same manner as in Example 4 except that heating was performed at 280 ° C. for 30 minutes in an air atmosphere in a clean oven, and a display device was prepared.

Example 8
6 g of Pigment Blue 60 (Indanthrone Blue, absorption maximum at 570 nm, 720 nm) and 2 g of Pigment Violet 19 (quinacridone red, absorption maximum at 510 nm, 550 nm, 600 nm) as components (d) were 20 g of γ-butyrolactone and N-methyl-2. Using a homogenizer together with 52 g of pyrrolidone and 50 g of glass beads, a dispersion treatment was performed at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration to obtain an organic pigment dispersion having a concentration of 10% by weight. In 40 g of the dispersion, 4 g of an alkali-soluble polymer (N), 1 g of a quinonediazide compound (H), and 4,4 ', 4 ", 4"'-(1,4-phenylenedimethylidene) tetrakisphenol which is a thermochromic compound (absorption) A mixed solution of 1 g (maximum 440 nm) and 3 g of γ-butyrolactone was added to obtain a varnish H1 of a positive photosensitive resin composition. Using a varnish H1, evaluation was performed in the same manner as in Example 4 except that heating was performed at 170 ° C. for 30 minutes in an air atmosphere in a clean oven and then at 320 ° C. for 60 minutes in a clean oven.

Example 9
Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum at 670 nm) as the component (d), 7 g, 4,4 ′, 4 ″ -methylidenetrisphenol (460 nm at absorption maximum) as a thermochromic compound, 2 g, 4,4 ', 4 ", 4"'-(1,4-phenylenedimethylidene) tetrakisphenol (absorption maximum 440 nm) 3 g Alkali-soluble polymer (P) 20 g, quinonediazide compound (G) 6.5 g, N-methyl-2-pyrrolidone 80 g and 73.5 g of 3-methyl-3-methoxybutyl acetate were dispersed together with 100 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration, thus the varnish of the positive photosensitive resin composition. Using varnish J1, the curing conditions were set in an air atmosphere in a clean oven. It was heated for 30 minutes at 170 ° C. under air, but heated followed by 350 ° C. for 30 minutes to create a display device evaluated in the same manner as in Example 4.

Comparative Example 1
Evaluation was performed in the same manner as in Example 1 except that 35 parts by weight of Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum at 670 nm) in Example 1 was not used, and a display device was prepared.

Comparative Example 2
Instead of using 30 parts by weight of Pigment Blue 60 (Indanthrone Blue, absorption maximum of 570 nm, 720 nm) and 10 parts by weight of Pigment Violet 19 (quinacridone red, absorption maximum of 510 nm, 550 nm, 600 nm) of Example 2, “NK-2612” was used. The evaluation was performed in the same manner as in Example 2 except that 40 parts by weight (absorption maximum 790 nm, manufactured by Hayashibara Biochemical Laboratory Co., Ltd.) was used to prepare a display device.

Comparative Example 3
Evaluation and display were performed in the same manner as in Example 3 except that Pigment Blue 15: 6 (Phthalocyanine Blue E, absorption maximum 670 nm) and Pigment Blue 60 (Indanthrone Blue, absorption maximum 570 nm, 720 nm) of Example 3 were not used. The device was created.

Comparative Example 4
A display device was prepared in the same manner as in Example 4 except that 1.25 g of 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane (absorption maximum 600 nm) was not used.

Comparative Example 5
A display device was prepared in the same manner as in Example 5 except that 4- [bis (4-hydroxyphenyl) methyl] 2-methoxyphenol (absorption maximum 470 nm) of Example 5 was not used.

Comparative Example 6
Instead of using 3 g of azochrome complex salt-based dye “Valifast Black 1807” (absorption maximum 580 nm) and 2.4 g of phthalocyanine-based dye “Valifast blue 2620” (absorption maximum 680 nm) (produced by Orient Chemical Co., Ltd., catalog 2002.2) of Example 6. In the same manner as in Example 6, except that 5.4 g of Pigment Yellow 12 (Disazo Yellow AAA, absorption maximum 420 nm) was used, a display device was prepared.

Comparative Example 7
In a γ-butyrolactone (274 g) solvent under a dry nitrogen stream, 10.7 g (0.049 mol) of pyromellitic dianhydride, 16.1 g (0.05 mol) of benzophenonetetracarboxylic dianhydride, 3, 6.2 g (0.025 mol) of 3'-diaminodiphenylsulfone, 14 g (0.07 mol) of 4,4'-diaminodiphenyl ether, 1.2 g (0.005 mol) of bis-3- (aminopropyl) tetramethylsiloxane ) Was reacted at 60 ° C. for 3 hours, 0.2 g (0.002 mol) of maleic anhydride was added, and the mixture was further reacted at 60 ° C. for 1 hour to obtain a precursor polyamic acid solution (polymer concentration: 15% by weight). %).

  2.5 g of 4,4 ', 4 ", 4"'-(1,4-phenylenedimethylidene) tetrakisphenol (absorption maximum 440 nm) which is a thermochromic compound, pigment blue 60 (indanthrone blue, absorption) 3 g of maximum 570 nm, 720 nm), 1 g of Pigment Violet 19 (quinacridone red, absorption maximum of 510 nm, 550 nm, 600 nm), 60 g of the polyamic acid solution, 14.5 g of N-methyl-2-pyrrolidone and 100 g of glass beads together with 100 g of glass beads at 7000 rpm. After 30 minutes of dispersion treatment, the glass beads were removed by filtration to obtain a varnish Q1 of a non-photosensitive resin composition.

  After coating on the substrate using the varnish Q1, prebaking was performed at 145 ° C. to form a polyimide precursor film. A positive photoresist was applied on the coating film and dried by heating at 90 ° C. to form a photoresist film. The film was exposed to ultraviolet light through a photomask, immersed in alkali development, and simultaneously developed with a photoresist film and etched with a polyimide precursor film to form openings. After the etching, the unnecessary photoresist film was removed by methylcellosolve acetate. The etched polyimide precursor film was heated in an air atmosphere at 290 ° C. for 60 minutes using a clean oven to form a polyimide insulating layer. The O.D. D was 1.8. The cross section of the boundary portion of the insulating layer had a forward tapered shape, and the taper angle θ was about 85 °.

  A light-shielding insulating layer was formed on non-alkali glass using varnish Q1, and the light resistance was evaluated. As a result, the optical density retention r was 95%.

  Thereafter, a simple matrix organic electroluminescent device was prepared in the same manner as in Example 1. When this display device was driven line-sequentially, the thin-film layer and the second electrode layer tended to be thinner at the boundary between the insulating layers because the cross-section of the insulating layer was a forward tapered shape with a taper angle of about 85 °. Brightness unevenness was observed in the region. The effective light emission area ratio S after the durability test was 80%.

Comparative Example 8
To 100 g of a negative photosensitive polyimide precursor varnish (UR-3100, manufactured by Toray Industries, Inc.), 10 g of 4,4 ', 4 "-methylidene trisphenol (a maximum absorption of 460 nm) of a thermochromic compound and Pigment Blue 15 of a dye : 6 (phthalocyanine blue E, absorption maximum 670 nm) and 6 g of Pigment Blue 60 (Indanthrone blue, absorption maximum 570 nm, 720 nm) were added to obtain a varnish R1 of a negative photosensitive resin composition. R1 was applied on the substrate on which the first electrode was formed by spin coating, and prebaked on a hot plate at 80 ° C. for 1 hour, and after exposing this coating film through a photomask, a developing solution (Toray ( Co., Ltd., DV-505) to develop by dissolving only the non-exposed areas and rinse with pure water. The insulating layer was formed by heating at 180 ° C. for 30 minutes and further at 220 ° C. for 30 minutes in the air atmosphere of No. 1. The OD of the obtained light-shielding insulating layer was 0.9. Was rectangular in shape, and the taper angle θ was about 90 °.

  Similarly, a light-shielding insulating layer was formed on non-alkali glass, and the light resistance was evaluated. As a result, the optical density retention r was 90%.

  Thereafter, a simple matrix organic electroluminescent device was prepared in the same manner as in Example 1. When the display device was driven line-sequentially, since the cross section of the insulating layer was rectangular, the thin film layer and the second electrode layer became thinner at the boundary between the insulating layers, and uneven brightness was observed in the light emitting region. The effective light emission area ratio S after the durability test was 70%.

Comparative Example 9
V259-PA (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), which is an alkali-soluble photoresist, is preliminarily added to the photocurable resin. A plastic resin containing 20 to 30% of crystal violet lactone (maximum absorption at 610 nm) as a color former and a resin containing 20 to 30% of an oil-soluble phenol resin as a color developer were used. As the thermoplastic resin used at this time, transparent polyethylene terephthalate was used. The concentration of the heat-sensitive material containing a color former or a developer in the photosensitive resin is as follows: photosensitive resin: color former-containing heat-sensitive material: developer-containing heat-sensitive material = 2: 1: 1. The varnish S1 was adjusted so that various materials were sufficiently dispersed in the photosensitive resin.

  The varnish S1 was applied on a substrate on which a first electrode was formed by spin coating, and prebaked on a hot plate at 80 ° C. for 3 minutes. Next, the film was exposed through a photomask, developed with an aqueous solution of sodium carbonate, and rinsed with pure water. Thereafter, heating is performed at 200 ° C. for 30 minutes using a hot plate to dissolve the heat-sensitive microcapsules added to the photocurable resin layer, and react the contained color former with the developer. The photocurable resin was blackened to form a resin black matrix insulating layer. The O.D. D was 2.0. The cross section of the boundary portion of the insulating layer was rectangular, and the taper angle θ was about 90 °.

  Similarly, a light-shielding insulating layer was formed on non-alkali glass, and the light resistance was evaluated. As a result, the optical density retention ratio r was 20%.

  Thereafter, a simple matrix organic electroluminescent device was prepared in the same manner as in Example 1. When the display device was driven line-sequentially, since the cross section of the insulating layer was rectangular, the thin film layer and the second electrode layer became thinner at the boundary between the insulating layers, and uneven brightness was observed in the light emitting region. The effective light emission area ratio S after the durability test was 70%.

  Table 1 shows the evaluation results of Examples 1 to 9 and Comparative Examples 1 to 9.

It is sectional drawing which shows the boundary part of an insulating layer.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 Substrate 2 First electrode 3 Insulating layer

Claims (14)

(A) an alkali-soluble resin, (b) a quinonediazide compound, (c) a thermochromic compound which develops color by heating and exhibits an absorption maximum at 350 nm or more and 700 nm or less, and (d) 500 nm or more without an absorption maximum at 350 nm or more and less than 500 nm. A positive photosensitive resin composition containing a compound having an absorption maximum at 750 nm or less. The composition according to claim 1, wherein the quinonediazide compound is an esterified quinonediazide compound. 3. The composition according to claim 1, wherein the component (a) is at least one selected from the following resins.
Phenol resin Polymer containing radically polymerizable monomer having alkali-soluble group The composition according to claim 1, wherein the component (a) comprises a structural unit represented by the general formula (1) as a main component.

(Wherein R ¹ is a divalent to octavalent organic group having two or more carbon atoms, R ² is a divalent to hexavalent organic group having two or more carbon atoms, R ³ and R ⁴ are And may be the same or different and represent hydrogen or an organic group having 1 to 20 carbon atoms, n is in the range of 5 to 100,000, p and q are integers of 0 to 4, r and s are Each is an integer from 0 to 2. p + q> 0.) The photosensitive resin composition according to claim 4, wherein the component (a) is at least one resin selected from resins having structural units represented by general formulas (2) to (5).

(Wherein R ¹ is a divalent to octavalent organic group having two or more carbon atoms, R ² is a divalent to hexavalent organic group having two or more carbon atoms, R ³ and R ⁴ are ^{May be the} same or different, hydrogen or an organic group having 1 to 20 carbon atoms, R ⁵ is a divalent organic group, X and Y are a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group A hydrocarbon group having at least one organic group selected from unsaturated hydrocarbon groups, having 1 to 10 carbon atoms, a nitro group, a methylol group, an ester group, a hydroxyalkynyl group, and a hydrocarbon having 1 to 10 carbon atoms. An organic group having one or more substituents selected from the group: n is in the range of 5 to 100,000, m is an integer of 0 to 10, p and q are integers of 0 to 4, r and s Is an integer from 0 to 2. p + q 0, it is.) The composition according to claim 5, wherein s is 0 in the general formulas (2) to (5). The composition according to any one of claims 1 to 6, wherein the component (c) is a thermochromic compound that develops color upon heating and exhibits an absorption maximum at 350 nm or more and 500 nm or less. The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (c) is a hydroxyl group-containing compound having a triarylmethane skeleton. The photosensitive resin composition according to any one of claims 1 to 8, wherein the cured film obtained after the heat treatment has an optical density of 0.5 or more. The photosensitive resin composition according to any one of claims 1 to 9, wherein the optical density of the cured film obtained after the heat treatment is maintained at 50% or more after 500 hours from irradiation with light. A method for producing a pattern, comprising a step of applying the photosensitive resin composition according to any one of claims 1 to 10 to a support substrate and drying, a step of exposing, a step of developing using an alkaline developer, and a step of heat treatment. . A patterned resin obtained by the method according to claim 11. An organic light emitting display having a pattern obtained from the composition according to claim 1. An organic light emitting display having the pattern according to claim 12.

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